Polyglycol ethers of higher second



Patented Aug. 15, 1944 POLYGLYCOL Erncns OF HIGHER SECOND- ABY, MONOHYDRIC ALCOHOLS Fritz Schlegel, Duesseldorf,

by mesnc assignments, to The Procter &

Gamble Company, Cincinnati, Ohio, a corporation of Ohio Germany, assignor,

No Drawing. Application December 5, 1940, Se-

rial No. 368,628. In Germany December 21,

6 Claims.

The present invention relates to polyglycol ethers of higher fatty alcohols active in lowering surface tension and a process for the production thereof.

It is well known that normal fatty acids, such as caproic acid, oenanthylic acid, caprylic acid, pelargonic acid, capric acid, n-undecylic acid, lauric acid, myristic acid, palmitic acid, margaric acid, and stearic acid, contain the carbon skeleton in the form of a straight chain. These carboxylic acids possess the general formula CH3 (CH2) 1;.COOH

whereby n represents a whole number from 4 to 16. The acids mentioned thus contain no branchings in their carbon skeleton. It is known that these fatty acids can be converted into ketones of the typ CH3 (CH2) n.CO(CH2)'m.CH3

whereby n and m represent whole numbers from .4 to 16. When pure individuals are converted into ketones, n may also be :m; but 11. and m are generally different, when mixtures of various fatty acids are converted into ketones.

It is known that these straight-chain ketones can be converted by hydrogenation into the corresponding secondary alcohols of the type CH3(CH2) 1;.CHOH. (CH2) ,m.CH3

whereby it and m have the values just described.

The conversion of the said secondary aliphatic straight-chain alcohols into neutral bodies active in lowering surface tension is one of the objects of the present invention.

A further object of the present invention is to convert these secondary alcohols into polyglycol ethers of the type CHa(CH2),..CH(CHz) W011i 1n represent a whole number from represents a whole number-from siderable quantities of ethyleneoxide in the presence of small quantities of caustic alkali or alkali alcoholates, forming valuable agents active in lowering surface tension, whereby, according to my invention, 6 to 20 mols ethylene oxide are used per mol alcohol.

According to my invention, conversion is effected in a closed vessel, preferably an autoclave equipped with a stirring device, ata temperature of from to 200 degrees C. The ethylene oxide may be admitted either in gaseous form, or in liquid form by means of a measuring pump. Conversion is initiated by raising the temperature to about 100 degrees C. According to the quantity of reagents present, the reaction mixture is heated to a temperature of up to 200 degrees C. by the heat of-reaction liberated.

Addition of ethylene oxide to the secondary alcohols takes place in the presence of an agent with an alkaline reaction, whereby the presence of 0.5 to 2 per cent of caustic potash or caustic soda, calculated on the alcohols, has proved to be the most efiective. But alkali alcoholates, such as sodium methylate, sodium ethylate, potassium ethylate, and the like, may also be used in the same proportions.

The reaction products are wax-like, If necessary, more particularly when the reagents used are of commercial grade, they can be freed by distillation in vacuo from readily volatile components and any quantities of alcohol not affected by the reaction. The said wax-like products are soluble in water, especially in hot water, giving a clear solution. They are able to emulsify oils, fats, and tarry compounds to a remarkable degree. They further possess an excellent property of wetting textiles, metals, glass, and porcelain, more particularly in conjunction with alkaline detergents. For that reason, the products prepared by addition of ethylene oxide to the said secondary alcohols are specially well suited for cleansing and degreasing articles soiled with oil or tar, or sheet metal and other materials treated by oil hardening, cold rolling, or other method of fabrication. The said wax-like products soluble in water can be successfully used in laundering and for the cleansing of very dirty cleaning cloths, workmens overalls, and textiles of a similar description used in industries'and trades. Apart from that surprisingly good property of wetting and cleansing, the detergent liquors prepared from the said products develop much less froth than do other polyglycol ethers with a neutral-reaction, which feature makes it possible to use them in washing and spraying distillation in vacuo.

rying it into practical effect, but my invention is not confined to this example.

Example A mixture of caproic acid. oenanthylic acid, caprylic acid, and pelargonic acid, produced by the oxidation of a straight-chain parafiin, is converted by ketonizing it in any familiar way into a mixture of aliphatic ketones with a chain length of from 11 to 17 carbon atoms. The said mixture of ketones is then converted by hydrogenation, for. example, according to the process of U. S. Patent No. 2,108,133, into a mixture came corresponding secondary alcoholsp 22.5 kilos of the said mixture of alcohols are gradually treated with 40 kilos ethylene oxide in the presence of 400 grams very finely ground caustic soda at an initial temperature of about 100 degrees C. in an autoclave equipped with an agitator, while stirring well. It can easily be demonstrated by measurement of the pressure that the ethylene oxide begins to be absorbed at a temperature of about 100 de rees C. The heat of reaction liberated serves to raise the temperature of the reaction mixture to from 170 to 180 degrees C., which temperature is maintained,

either by cooling or by additional application of heat, until the ethylene oxide has been completely absorbed.

After completion of the reaction, the reaction mixture is freed from unconverted alcohol by i The residue isa wax-like product which is admirably adapted for the preparation of a detergent liquor for degreasing light metals or oil-hardened iron parts. Such a detergent liquor should contain preferably a mix- Now what I claim is:

1. As a new product, compounds having the whereby n and m represent respectively a Whole number from 4 to 16, and a: a whole number from 5 to 19.

2. As a new product a wax-like mass consisting of polyglycol ethers of higher molecular, monohydric secondary, straight chain aliphatic alcohols. having at least 11 carbon atoms.

3. Compounds of waxy consistency having high wetting powers but low foaming power consisting of polyglycol ethers of monohydric secondary straight chain aliphatic alcohols having from 11 to 35 carbon atoms in the chain.

4. The process of producing polyglycol ethers having high wetting powers and low foaming power from higher molecular, monohydric secondary straight chain aliphatic alcohols derived by the hydrogenation of ketones obtained from fatty acids having from 6 to 18 carbon atoms in the molecules, which comprises heating such alcohols with from 6 to 20 mols of ethylene oxide per mol of alcohol in a closed container at a temperature of .to 200 C. in the presence of an alkalinity-imparting agent.

5. The process of producing compounds having high wetting power and low foaming power from compounds having hydrocarbon chains of inadequate lipophilic characteristics, which comprises forming ketones from fatty acids having from 6 to 9 carbon atoms, hydrogenating the ketones thereby forming secondary alcohols and reacting the alcohols with ethylene oxide in a quantity between 6 'to 20 mols to each mol of alcohol in a closed container at a temperature of 100 to 200 C. in 'the presence of caustic soda to form polyglycol ethers of said alcohols thereby imparting hydrophilic qualities to balance the lipophilic qualities of the hydrocarbon chains of the alcoholic component.

6. Compounds of waxy consistency having high wetting powers but low foaming power consisting of polyglycol ethers of .monohydric secondary straight chain aliphatic alcohols having from 11-17 carbon atoms in the chain. 

